Method for the control of insects

ABSTRACT

A method has been discovered for the control of arthropod pests which comprises treating the pest with an effective amount of selected fluorocarbons.

This application is a continuation of Ser. No. 256,237 filed Oct. 11, 1988, now U.S. Pat. No. 4,921,696 which was a continuation of Ser. No. 758,856 filed July 26, 1985, now abandoned, which was a continuation of Ser. No. 455,727 filed Jan. 5, 1983, now abandoned, and a continuation-in-part of Ser. No. 598,908 filed Apr. 10, 1984, now abandoned, which was a continuation of Ser. No. 361,501 filed Mar. 25, 1982, now abandoned.

PRIOR ART

Discovering pesticides that are effective against a broad range of insect pests and that also can be used safely on crop lands and pastures has long been a problem. One such problem area has been in the control of ants and related insects. Particularly destructive are fire ants (such as Solenopsis invicta) which sting humans and livestock, feed on crop seedlings and germinating seeds thereby reducing yields, and damaging equipment which strike their mounds. Requirements for an effective pesticide formulation for the control of fire ants has been characterized as being (1) not repellent to the ants, (2) readily transferable from one ant to another, and (3) exhibiting delayed toxicity. Repellency can reduce or negate the effectiveness of a toxicant because the ants will avoid the treated bait. The treated bait must be transferable either by carrying it back to the next or by trophallaxis, and the toxicity must be delayed because foraging ants constitute only a small percentage of the total colony and must survive long enough to pass the toxicant onto the main colony population, especially the queen. It is preferable that the formulations exhibit delayed toxicity over a wide range of pesticide concentration because the active ingredient becomes diluted during trophallaxis (Banks et al, ARS-S-169, Oct. 1977). Presently only one commercially available pesticide (Amdro U.S. Pat. No. 4,152,436) is registered as a bait for outdoor control of fire ants such as Solenopsis invicta, S. xyloni, S. richteri, and other ants including Pheidols megacephala and Iridomyrmex humilis. Amdro is also effective against Lepidopterous larvae. However, it cannot be applied to edible crops. The insecticide Mirex (U.S. Pat. No. 3,220,921) is also known to be effective against fire ants, but is no longer registered for use.

SUMMARY OF THE INVENTION

We have discovered a method and a composition for the control of a population of arthropods including ants, cockroaches, flies, mosquitoes, and termites. The method comprises treating the pests with an effective amount of toxicant substance or mixture of substances of the formula

    R.sub.f SO.sub.2 A

wherein R_(f) is a fluoroaliphatic radical containing up to 20 carbon atoms and A is a structurally compatible residue, or agriculturally acceptable salts of the toxicant substance or substances. The compositions in accordance with the invention comprise the above toxicant substance or mixture of substances and a bait component.

The fluoroaliphatic radical, R_(f), if a fluorinated, monovalent moiety which is straight chain, branched chain, and if sufficiently large, cyclic, or combinations thereof, such as alkylcycloaliphatic radicals. The skeletal chain can include catenary oxygen and/or trivalent nitrogen nitrogen hetero atoms bonded only to carbon atoms, such hereto atoms providing stable linkages between fluorocarbon groups and not interferring with the chemically inert character of the R_(f) radical. While R_(f) can have a large number of carbon atoms, compounds where R_(f) is not more than 20 carbon atoms will be adequate and preferred since large radicals usually present a less efficient utilization of fluorine than is possible with smaller R_(f) radicals. Generally, R_(f) will have up to 20 carbon atoms, preferably 5 to about 12. The terminal porton of the R_(f) group has preferably at least three fully fluorinated carbon atoms, e.g., CF₃ CF₂ CF₂ --, and the preferred compounds are those in which the R_(f) group is fully or substantially completely fluorinated, as in the case where R_(f) is perfluoroalkyl, C_(n) F_(2n+1).

In the above formula A is structurally compatible residue (i.e., capable of being linked to the SO₂ radical which includes the radicals NR₁ R₂ and OR₄ wherein R₁ and R₂ are selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, aralkyl, aroyl, acyl, cycloalkyl, cycloalkenyl, cycloalkynyl, a heterocyclic ring containing atoms selected from the group consisting of C, N, S or O, hydroxyalkyl, haloalkyl, aminoalkyl, carboxyalkyl salts, esters and amides, or a group of the structure --(C_(x) H_(2x) O)_(n) (C_(y) H_(2y) O)mR₃ wherein n+m=1-20, x and y are 1-4 and R₃ is selected from the same group as R₁ and R₂ ; and wherein R₄ is H, aryl, a heterocyclic ring or an alkaline earth, alkali metal, organic amine or ammonium cation. The formula NR₁ R₂ also includes radicals in which N, R₁ and R₂ are taken together to form a ring the atoms of which are selected from the group consisting of C, N, S or O.

The salts of the invention are generally metal, ammonium or organic amine and quaternary amine salts and can be prepared by treating the acid-form compound with an appropriate base under mild conditions. Among the metal salts of the invention are alkali metal (e.g., lithium, sodium and potassium), alkaline earth metal (e.g., barium, calcium and magnesium) and heavy metal (e.g., zinc and iron) salts as well as other metal salts such as aluminum. Appropriate bases for use in preparing the metal salts include metal oxides, hydroxides, carbonates, bicarbonates and alkoxides. Some salts are also prepared by cation exchange reaction (by reacting a salt of the invention with an organic or inorganic salt in a cation exchange reaction). The organic amine salts include the salts of aliphatic (e.g., alkyl), aromatic and heterocyclic amines, as well as those having a mixture of these types of structures. The amines useful in preparing the salts of the invention can be primary, secondary or tertiary and preferably contain not more than 20 carbon atoms. Such amines include, for example, morpholine, methyl cyclohexylamine, glucosamine, amines derived from fatty acids, etc. The amine and ammonium salts can be prepared by reacting the acid form with the appropriate organic base or ammonium hydroxide. Any of the salts of the types set out above are agriculturally acceptable, the one chosen depending upon the particular use and upon the economics of the situation. Of particular utility are the alkali metal, alkaline earth, ammonium and amines salts.

The salts of the invention are frequently formed by reacting the precursors in aqueous solution. This solution can be evaporated to obtain the salt of the compound, usually as a dry powder. In some cases, it may be more convenient to use a non-aqueous solvent such as aldohols, acetones, etc. The resulting solution is then utilized in formulations which are treated to remove the solvent, for example, by evaporation under reduced pressure.

These pesticides which are suitable for use in the invention fulfill the above mentioned requirements for fire ant control and in addition, possess very little mammalian toxicity. They are also effective against other arthropods.

DETAILED DESCRIPTION OF THE INVENTION

Arthropod pests are suitably treated in accordance with the invention in any manner known to the prior art which is compatible with the above described toxicant compounds and mixtures. Suitable treatments include applying the toxicants as sprays in solutions, emulsions and dispersions; in traps with or without pheromone attractants and the like; and in bait formulations scattered in the vicinity of nests or in crop lands.

Substances suitable for use in this invention must be effective for at least one species of arthropod. However, these are several factors which may affect the effectiveness of specific substances with specific insects and with specific treatment techniques. These factors include:

1. Odor repellency.

2. Taste repellency.

3. Solubility in carriers such as solvents and baits.

4. Enzymatic effects.

5. Degradation by atmospheric oxygen, UV radiation and the like.

Using the invention for control of ants, in particular imported fire ants, it is preferably to prepare bait formulations into which the toxicants can be incorporated. The term "bait" is understood by those skilled in the art to be any substance that will entice the insect to ingest the toxicant. Suitable baits include edible oils and fats, vegetable seen meals, meal-by-products such as blood, fish meal, syrups, honey, sucrose and other sugars, peanut butter, cereals and the like (see U.S. Pat. No. 3,220,921). Preferred baits for fire ants are mixtures of edible oils (as solvents for the toxicant compounds) with granular carries such as corncob grits, pregel defatted corn grits and the like. These impregnated granular bait formulations readily fall to the ground when dispersed by a real or ground applicators where the ants forage, when found by the ants they are carried into the next where the toxicants are ingested and distributed to workers and queen.

These compounds of the invention are known; but they are not known to be useful in pesticide formulations. Disclosures relevant to their preparation are found in the following U.S. Pat. Nos. 2,803,615, 2,346,612, 2,732,378, 2,732,378, 2,759,019, 2,803,656, 2,915,554, 3,398,182 and 3,787,351.

The tests in the following examples indicate the effectiveness of the invention but are not intended to limit the invention's scope which is defined by the claims. All percentages and parts are by weight unless otherwise specified.

For fire ants any compound showing % mortality which is significantly greater than the bait without the toxicant is considered to be effective for the purposes of this invention. The use of preferred toxicants should result in less than 15% mortality at 24 hours and more than 50% and most preferably more than 85% mortality by the end of the test. The preferred compounds are also should have at least a 10-fold difference between maximum and minimum dosages exhibiting delayed toxicity.

EXAMPLE 1

Each compound to be screened for fire ant toxicity was tested in 3 replications of 20 worker ants (Solenopsis invicta) which were placed in 30 ml cups for 14 days.

Cotton swabs saturated with soybean oil containing 1.0% of a test compound were offered to the ants in the cups for a 24 hour period. The swabs removed and the ants remained without food for 24 hours. Cotton swabs saturated with SBO only were then placed in the cups and left there for the remainder of the testing period. Mortality counts were recorded for the test compounds and for a standard fire ant toxicant, Table 1

EXAMPLE 2

Some of the compounds tested in Example 1 were retested as in Example 1 at concentrations of 0.01%, 0.10% and 1.0%, Table 2.

EXAMPLE 3

Some of the compounds listed in Table 1, which were not readily soluble in SBO were retested in the same manner as in Example 1 with the exception that SBO was replaced with a 1:1 v/v mixture of honey and water, Table 3.

EXAMPLE 4

Some of the preferred compounds from Example 2 were tested against duplicate laboratory colonies of fire ants.

The colonies consisted of a queen, eggs, larvae, pupae and greater than 40,000 workers. The test compounds were dissolved in SBO at 1.0% concentration and impregnated on pregel defatted corn grits so that the corn grits contained 30% of the total bait weight.

Five grams of the bait was made available to each colony for 4 days. The bait was removed and the colonies fed a standard diet for the remainder of the test which consisted on 1:1 honey-water mixture, boiled eggs and frozen fly pupae and cockroaches. Two colonies were treated with bait without toxicant as a control. Observation on the status of the queen and workers are recorded in Table 4. The ultimate fate of the colony is indicated as QD (queen dead) or CN (colony normal), Table 4.

EXAMPLE 5

Mixed sexes of adult house flies (Musca domestica) from an insecticide-resistant laboratory strain were fed after emergence exclusively on a fly food bait (6parts sugar, 6 parts powdered nonfat dry milk, and 1 part powdered egg yolk) containing 1% of the test compounds. The bait was prepared by adding 10 ml of a solution or suspension of the test compound in a volatile solvent to 10 g of fly food in a small container. The solvent was allowed to evaporate for 4 to 6 hours, then the treated fly food was repulverized. The container of treated fly food and a container of water was placed in a cage with 100 newly emerged adult flies. Percent mortality for two replicate tests was determined after 3 days and compared to the results of feeding untreated fly food, Table 5.

Some of the above compounds may be more effective than the data indicates. If solubilities were poor in the SBO or honey-water formulation, concentrations of toxicants may not have reached the desired level. Many of these compounds showing poor effectiveness may be highly effective in other formulations.

EXAMPLE 6

Compounds 29757, 29758 and 29759 (see Table 1 for structures) were each dissolved in SBO at 1% concentration. Bait was prepared by impregnating the SBO mixture on pregel defatted corn grits so that the corn grit mixture contained 30% SBO mixture and 0.3% test compound. Compound 29759 was also used at 2.5% concentration so that it was 0.75% of the total bait weight.

Treated baits were scattered by tractor on field plots containing a number of active fire ant mounds at a concentration of one pound per acre. Other plots containing fire ant mounds were treated in the same manner with untreated pregel defatted corn grits and with grits treated with a standard fire ant toxicant as control. Results were evaluated as described by D. P. Harlan, W. H. Bands and C. E. Stringer, Southwest Entomologiest, Vol 6, pp. 150-157, 1981, Table 6.

EXAMPLE 7

Compounds 29756, 29757, 29759 and 29778 were used to treat Orlando normal colonies of American cockroaches (Periplaneta americana) each containing 10 adults of mixed sexes as described by G. S. Burden, Pest Control Vol. 48, pp 22-24, 1980. A bait was formulated which consisted 2.0% of the above compounds or a standard cockroach toxicant (trichlorfon). Untreated 3:1 mixture of cornmeal and powdered sugar was used as a control. A container with 2 grams of normal diet (Purina Lab Chow 5001) were placed in each arena with the cockroaches and left until the test was ended. Percent mortality is shown in Table 7.

EXAMPLE 8

Orlando normal colonies of German cockroaches (Blattella germanica) containing 25 adults were treated in the same manner as in Example 7. Results are shown in Table 8.

EXAMPLE 9

Twenty-five late 3rd- and early 4th-stage larvae of Anopheles quadrimaculatus were placed in a 500 ml glass jar (9×8.5 cm diam) containing 100 ml of well water, 0.05 g ground hog supplement for larval food, and a known amount of the candidate compound in not more than 1.0 ml acetone. The jars were covered with cloth netting and held in constant temperature incubators at 26.7°-28.9° C. (80°-84° F.) and 65-75% RH; a low level of illumination (ca. 0.5 footcandles inside the incubators) was maintained during nonworking hours. Seven days after set up, the jars were examined for the number of dead pupae, the number of adults that were dead or unable to complete eclosion, and the number of exuviae. The live adults were observed for gross abnormalties. Tests were replicated for at least 1 concn, and a standard larvicide, methoprene, was used as a control with each test series.

Several concns, of each compound were tested so that a dose-response relationship could be established. Using the Statistical Analysis System supported by NERDC, the resulting data were corrected for control mortality (Abbott's formula) and a probit analysis was made using log transformed mortality data. This analysis provided estimates for the LC-50 and LC-90, in ppm, for the compound.

EXAMPLE 10

Compounds were screened as mosquito larvicides (Insect Growth Regulators, IGR) by exposing early 4th-instar larvae of Anopheles quadrimaculatur to solutions or suspensions of the compounds in water (duplicate tests). The compounds were dissolved in acetone and added to water; water-soluble compounds remained in solution and the others became finely divided suspensions. Mosquito larvae were added to the treated water and mortality was determined after 24 hours of exposure. The compounds were initially tested at concns. of 10 and 1 parts per million. If 50% mortality occurred at 1 ppm, additional test were conducted with lower concns. A standard larvicide, temephos (Abate), was tested as a control concurrently.

Results are shown in Table 10.

The following indicates the criteria for compounds tested against mosquitoes:

    ______________________________________                                         Classification of IGR's Against Mosquitoes                                     Class     Criteria         LC-90 (ppm)                                         ______________________________________                                         1         Ineffective at screening                                                                        >1.000                                                        dose                                                                 2         Partially effective but                                                                         0.101-1.000                                                   not promising                                                        3         Effective enough to justify                                                                     0.021-0.100                                                   full investigation                                                   4         Exceptional      <0.020                                              ______________________________________                                    

Results are shown in Table 9.

                                      TABLE I                                      __________________________________________________________________________                                     Mortality at Specified Days                                                    %                                              Number                                                                              Structure                  1 2  3  6  8 10 14                             __________________________________________________________________________     29752                                                                                ##STR1##                  2 3  3  3  3 3  10                             29753                                                                                ##STR2##                  0 0  0  8  65                                                                               87 93                             29754                                                                                ##STR3##                  0 0  0  3  32                                                                               72 93                             29755                                                                                ##STR4##                  0 0  0  17 38                                                                               87 97                             29756                                                                                ##STR5##                  3 3  13 73 90                                                                               97 98                             29757                                                                                ##STR6##                  33                                                                               88 100                                       29758                                                                                ##STR7##                  18                                                                               88 100                                       29759                                                                               C.sub.8 F.sub.17 SO.sub.2 NH.sub.2                                                                        18                                                                               63 85 88 97                                                                               100                               29760                                                                                ##STR8##                  0 0  0  0  0 3  70                             29761                                                                                ##STR9##                  2 2  2  2  2 2  10                             29762                                                                                ##STR10##                 2 2  2  2  2 2  10                             29763                                                                                ##STR11##                 2 3  3  7  7 13 40                             29764                                                                                ##STR12##                 0 0  0  0  0 0  17                             29765                                                                                ##STR13##                 0 0  0  2  17                                                                               47 83                             29766                                                                               Adduct from                0 0  0  3  3 3  23                                   ##STR14##                                                                     1 mole C.sub.18 H.sub.37 OH and                                                 ##STR15##                                                                29767                                                                                ##STR16##                 0 0  0  2  25                                                                               80 97                             29768                                                                                ##STR17##                 0 0  0  7  42                                                                               87 97                             29769                                                                                ##STR18##                 0 0  13 70 90                                                                               95 98                             29770                                                                                ##STR19##                 68                                                                               100                                          29771                                                                                ##STR20##                 0 2  2  48 90                                                                               100                               29772                                                                                ##STR21##                 0 0  0  2  5 17 62                             29773                                                                                ##STR22##                 0 2  2  2  2 12 43                             29774                                                                                ##STR23##                 0 0  0  0  2 3  7                              29775                                                                                ##STR24##                 0 0  3  3  3 5  13                             29776                                                                                ##STR25##                 0 0  0  0  0 3  23                             29777                                                                                ##STR26##                 0 0  5  47 82                                                                               98 100                            29778                                                                                ##STR27##                 0 0  70 93 98                                                                               98 100                            29779                                                                               C.sub.2 F.sub.5 C.sub.6 F.sub.10 SO.sub.3 K                                                               0 2  2  7  7 10 15                             29780                                                                               C.sub.7 F.sub.15 CO.sub.2 NH.sub.4                                                                        0 0  2  2  3 3  5                              29781                                                                                ##STR28##                 0 0  0  18 40                                                                               80 97                             29782                                                                                ##STR29##                 0 0  5  15 53                                                                               83 100                            50950                                                                               C.sub.8 F.sub.17 SO.sub.3 K                                                                               0 0  0  0  0 0  0                              10700                                                                                ##STR30##                 0 3  7  58 70                                                                               80 87                             10701                                                                                ##STR31##                 0 15 80 97 98                                                                               98 100                            10702                                                                               C.sub.6 F.sub.13 SO.sub.2 NH.sub.2                                                                        3 8  40 80 83                                                                               85 92                             10703                                                                               CF.sub.3 SO.sub.2 NH.sub.2 3 13 25 58 70                                                                               72 72                             10704                                                                                ##STR32##                 68                                                                               97 100                                       10705                                                                                ##STR33##                 2 2  2  3  8 15 30                             10706                                                                                ##STR34##                 0 0  0  0  3 5  10                             10707                                                                               C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        17                                                                               100                                          10708                                                                                ##STR35##                 0 2  2  7  7 7  7                              10709                                                                                ##STR36##                 0 2  2  48 53                                                                               72 85                             10710                                                                                ##STR37##                 2 25 55 90 95                                                                               98 98                             10711                                                                                ##STR38##                 0 12 40 93 97                                                                               98 98                             10712                                                                                ##STR39##                 8 88 100                                       10713                                                                                ##STR40##                 0 0  0  0  0 0  5                              10714                                                                                ##STR41##                 75                                                                               82 82 90 90                                                                               92 93                             10715                                                                                ##STR42##                 68                                                                               82 85 92 92                                                                               92 100                            10716                                                                                ##STR43##                 52                                                                               63 63 77 83                                                                               88 90                             10717                                                                                ##STR44##                 23                                                                               87 98 100                                    10718                                                                                ##STR45##                 0 2  3  3  3 5  12                             10719                                                                                ##STR46##                 2 5  7  7  7 7  7                              10720                                                                                ##STR47##                 0 0  0  3  7 12 32                             10721                                                                               C.sub.8 H.sub.17 SO.sub.2 NH.sub.2                                                                        5 7  8  12 12                                                                               12 12                             10722                                                                                ##STR48##                 0 0  0  2  3 3  3                              10723                                                                                ##STR49##                 2 2  2  5  5 7  8                              10724                                                                                ##STR50##                 0 0  0  2  2 2  3                              10725                                                                                ##STR51##                 0 0  0  0  7 18 52                             10726                                                                                ##STR52##                 0 0  0  0  0 0  0                              10727                                                                               C.sub.8 F.sub.17 SO.sub.3 H                                                                               0 3  3  12 12                                                                               22 22                             10728                                                                               C.sub.6 F.sub.13 SO.sub.3 H                                                                               0 0  0  3  7 7  8                              10729                                                                                ##STR53##                 0 0  0  7  13                                                                               25 50                             10730                                                                                ##STR54##                 0 2  2  3  20                                                                               30 62                             10731                                                                               C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.4 OH).sub.2                                                     0 0  0  2  5 10 35                             10732                                                                                ##STR55##                 0 0  0  2  2 2  5                              10733                                                                                ##STR56##                 5 50 70 93 97                                                                               98 100                            10734                                                                                ##STR57##                 2 3  5  5  8 20 57                             10735                                                                               C.sub.8 F.sub.17 C.sub.2 H.sub.4 SH                                                                       3 3  3  3  3 5  5                              10736                                                                               [CF.sub.2 CF.sub.2 SO.sub.2 NH.sub.2 ].sub.2                                                              0 2  2  3  3 3  5                              10737                                                                                ##STR58##                 0 3  3  10 10                                                                               10 25                             10738                                                                                ##STR59##                 3 3  3  5  5 5  5                              10739                                                                                ##STR60##                 0 0  0  2  2 2  2                              10740                                                                                ##STR61##                 0 0  0  0  0 3  3                              10741                                                                                ##STR62##                 3 3  3  32 35                                                                               38 48                             10742                                                                               CF.sub.3 SO.sub.2 N(CH.sub.3).sub.2                                                                       82                                                                               82 82 82 82                                                                               82 90                             10743                                                                                ##STR63##                 0 0  0  12 13                                                                               15 20                             10744                                                                               C.sub.2 F.sub.5 SO.sub.2 NH.sub.2                                                                         3 17 22 35 40                                                                               45 50                             10745                                                                               C.sub.4 F.sub.9 SO.sub.2 NH.sub.2                                                                         0 0  0  3  3 3  5                              10746                                                                                ##STR64##                 0 5  8  13 15                                                                               17 23                             10747                                                                                ##STR65##                 0 0  0  32 48                                                                               53 73                             10748                                                                                ##STR66##                 3 13 17 37 42                                                                               47 85                             10749                                                                                ##STR67##                 2 5  5  38 57                                                                               80 88                             10750                                                                               C.sub.8 F.sub.17 SO.sub.3.sup.⊖  .sup.⊕ N(C.sub.2                  H.sub.5).sub.4             0 0  0  3  3 3  7                              10751                                                                               C.sub.6 F.sub.10 (CH.sub.2 OH).sub.2                                                                      2 5  5  23 28                                                                               32 58                                  (Cyclic)                                                                  10752                                                                               FCH.sub.2 SO.sub.2 NH.sub.2                                                                               0 0  2  30 33                                                                               43 53                             10753                                                                               HCF.sub.2 SO.sub.2 NH.sub.2                                                                               0 2  2  13 18                                                                               20 30                             10754                                                                               CF.sub.3 CH.sub.2 SO.sub.2 NH.sub.2                                                                       0 0  0  2  3 5  13                                  Standard                   0 12 97 100                                         SBO                        0 0  0  5  8 9  13                             __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________                             Conc.                                                                              Percent Mortality at Specified Days                Number                                                                              Structure          %   1   2   3   6   8   10  14  17  21                 __________________________________________________________________________     29753                                                                                ##STR68##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 0                                                                              0 0 2                                                                              0 0 52                                                                             3 0 87                                                                             7 0 98                                                                             7 3 99                                                                             13 7 100                                                                           20 27              29754                                                                                ##STR69##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 2 0                                                                              0 2 0                                                                              0 3 0                                                                              0 3 0 3 40                                                                             0 25 92                                                                            0 48 98                                                                            2 78 100           29755                                                                                ##STR70##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 0                                                                              0 0 0                                                                              5 2 12                                                                             7 2 45                                                                             12 7 80                                                                            15 10 95                                                                           22 23 98                                                                           28 40 98           29756                                                                                ##STR71##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 2                                                                              2 0 10                                                                             5 2 83                                                                             8 5 85                                                                             8 30 95                                                                            8 75 100                                                                           10 85                                                                              13 92              29757                                                                                ##STR72##         0.01 0.1 1.0                                                                       0 0 25                                                                             0 0 100                                                                            0 2 0 80                                                                               2 97                                                                               2 97                                                                               10 98                                                                              22 98                                                                              50 100             29758                                                                                ##STR73##         0.01 0.1 1.0                                                                       0 0 17                                                                             0 0 93                                                                             2 7 100                                                                            3 88                                                                               7 97                                                                               7 98                                                                               7 100                                                                              23  40                 29759                                                                               C.sub.8 F.sub.17 SO.sub.2 NH.sub.2                                                                0.01                                                                               0   0   0   3   7   7   10  20  23                                         0.1 0   0   0   2   33  77  92  95  98                                         1.0 43  85  98  100                                    29765                                                                                ##STR74##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 0                                                                              0 0 0                                                                              0 0 0 0 2                                                                              0 0 32                                                                             0 2 77                                                                             0 13 88                                                                            0 15 100           29767                                                                                ##STR75##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 0                                                                              0 0 0                                                                              0 2 2                                                                              0 2 42                                                                             3 3 83                                                                             3 8 100                                                                            3 18                                                                               3 42               29769                                                                                ##STR76##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 0                                                                              0 0 32                                                                             3 2 100                                                                            7 3 7 5 10 10                                                                              13 25                                                                              17 48              29770                                                                                ##STR77##         0.01 0.1 1.0                                                                       2 0 47                                                                             2 2 98                                                                             3 2 98                                                                             5 5 100                                                                            7 7 8 17                                                                               10 48                                                                              13 58                                                                              15 70              29771                                                                                ##STR78##         0.01 0.1 1.0                                                                       0 2 0                                                                              0 2 0                                                                              0 2 2                                                                              0 7 87                                                                             0 10 98                                                                            8 17 98                                                                            10 20 98                                                                           13 32 98                                                                           18 58 98           29772                                                                                ##STR79##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 2                                                                              2 0 2                                                                              2 0 2 0 2                                                                              2 3 40                                                                             2 3 87                                                                             2 15 97                                                                            2 45 100           29773                                                                                ##STR80##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 0                                                                              0 0 0                                                                              0 0 3                                                                              0 0 5                                                                              0 0 23                                                                             0 0 37                                                                             0 3 45                                                                             0 17 60            29776                                                                                ##STR81##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 0                                                                              0 0 0                                                                              0 2 0                                                                              2 2 0                                                                              2 2 0                                                                              2 2 0                                                                              2 2 7                                                                              2  3 35            29777                                                                                ##STR82##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 2                                                                              0 0 3                                                                              5 0 78                                                                             5 2 97                                                                             5 2 100                                                                            7 20                                                                               13 50                                                                              17 80              29778                                                                                ##STR83##         0.01 0.1 1.0                                                                       2 0 0                                                                              3 2 2                                                                              3 3 17                                                                             8 10 92                                                                            8 10 100                                                                           8 52                                                                               13 67                                                                              15 80                                                                              18 88              29779                                                                               C.sub.2 F.sub.5 C.sub.6 F.sub.10 SO.sub.3 K                                                       0.01                                                                               0   0   0   2   2   2   2   2   2                                          0.1 0   0   0   0   2   3   3   3   3                                          1.0 0   0   0   0   2   2   5   5   7                  29781                                                                                ##STR84##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 0                                                                              0 0 0                                                                              2 3 77                                                                             2 3 93                                                                             5 5 95                                                                             5 8 100                                                                            7 12                                                                                7 23              29782                                                                                ##STR85##         0.01 0.1 1.0                                                                       0 0 0                                                                              0 0 0                                                                              2 0 0                                                                              2 0 45                                                                             2 2 67                                                                             2 2 88                                                                             2 8 98                                                                             2 40 100                                                                           3 60               10700                                                                                ##STR86##         0.01 0.1 1.0                                                                       2 2 0                                                                              3 3 2                                                                              3 3 7 8 75                                                                             7 12 88                                                                            7 40 93                                                                            8 70 98                                                                            12 82 100                                                                          15 95              10701                                                                                ##STR87##         0.01 0.1 1.0                                                                       0 0 23                                                                             0 0 87                                                                             0 0 100                                                                            0 18                                                                               0 65                                                                               0 83                                                                               0 95                                                                               2 97                                                                               7 98               10702                                                                               C.sub.6 F.sub.13 SO.sub.2 NH.sub.2                                                                0.01                                                                               0   0   0   2   2   2   2   5   12                                         0.1 3   7   7   7   7   17  63  77  92                                         1.0 0   3   30  67  75  87  95  98  100                10703                                                                               CF.sub.3 SO.sub.2 NH.sub.2                                                                        0.01                                                                               0   0   0   3   3   5   7   8   17                                         0.1 3   3   3   5   5   5   17  27  58                                         1.0 2   8   18  33  42  50  67  73  82                 10704                                                                                ##STR88##         0.01 0.1 1.0                                                                       0 2 87                                                                             2 2 98                                                                             3 2 98                                                                             7 3 98                                                                             7 3 98                                                                             8 3 100                                                                            8 3 15 3                                                                               27 10              10707                                                                               C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                0.01                                                                               0   0   0   2   5   10  20  50  60                                         0.1 0   7   13  78  92  98  100                                                1.0 30  100                                            10709                                                                                ##STR89##         0.01 0.1 1.0                                                                       5 2 0                                                                              5 2 0                                                                              5 2 0                                                                              5 2 2                                                                              5 3 45                                                                             5 5 60                                                                             15 43 90                                                                           15 73 93                                                                           30 87 100          10710                                                                                ##STR90##         0.01 0.1 1.0                                                                       2 3 13                                                                             2 3 53                                                                             2 3 80                                                                             2 48 100                                                                           2 60                                                                               2 78                                                                               12 93                                                                              37 98                                                                              75 100             10711                                                                                ##STR91##         0.01 0.1 1.0                                                                       2 3 23                                                                             2 3 57                                                                             2 3 72                                                                             3 18 88                                                                            5 42 100                                                                           5 85                                                                               5 97                                                                               7 98                                                                               28 100             10712                                                                                ##STR92##         0.01 0.1 1.0                                                                       2 0 83                                                                             2 0 97                                                                             2 10 100                                                                           2 75                                                                               2 93                                                                               3 98                                                                               5 100                                                                              27  65                 10714                                                                                ##STR93##         0.01 0.1 1.0                                                                       0 0 83                                                                             0 2 87                                                                             0 2 88                                                                             2 8 95                                                                             3 53 97                                                                            3 70 97                                                                            7 93 100                                                                           17 95                                                                              27 98              10715                                                                                ##STR94##         0.01 0.1 1.0                                                                       2 0 88                                                                             2 0 92                                                                             2 0 93                                                                             2 18 97                                                                            2 63 98                                                                            2 87 98                                                                            3 90 98                                                                            12 95 98                                                                           27 98 100          10716                                                                                ##STR95##         0.01 0.1 1.0                                                                       2 0 78                                                                             5 3 83                                                                             5 3 87                                                                             8 12  100                                                                          8 40                                                                               8 70                                                                               8 93                                                                               13 97                                                                              27 97              10717                                                                                ##STR96##         0.01 0.1 1.0                                                                       0 0 100                                                                            0 7 0 33                                                                               8 77                                                                               8 90                                                                               13 92                                                                              25 100                                                                             37  57                 10733                                                                                ##STR97##         0.01 0.1 1.0                                                                       0 0 57                                                                             0 0 87                                                                             0 2 98                                                                             0 22 100                                                                           3 83                                                                               3 95                                                                               5 97                                                                               23 100                                                                             47                 10742                                                                               CF.sub.3 SO.sub.2 N(CH.sub.3).sub.2                                                               0.01                                                                               0   0   0   0   0   3   12  13  30                                         0.1 0   0   3   3   5   8   17  35  53                                         1.0 88  90  90  97  98  98  98  98  100                10749                                                                                ##STR98##         0.01 0.1 1.0                                                                       2 5 2                                                                              3 5 5                                                                              3 8 5                                                                              3 15 38                                                                            3 20 57                                                                            5 23 80                                                                            8 40 88                         Copolymer of                                                                    ##STR99##         0.01 0.1 1.0                                                                       -- 0 3                                                                             -- 8 3                                                                             -- 10 7                                                                            -- 18 13                                                                           -- 18 15                                                                           -- 20 22                                                                           -- 52 47                                                                           -- -- --                                                                           -- 87 73                 ##STR100##                                                                     ##STR101##                                                                    (C.sub.3 H.sub.6 O).sub.22 (C.sub.2 H.sub.4 O).sub.10                           ##STR102##                                                                    50% Copolymer of                                                                ##STR103##        0.01 0.1 1.0                                                                       -- 2 5                                                                             -- 3 7                                                                             -- 5 7                                                                             -- 10 15                                                                           -- 12 22                                                                           -- 13 25                                                                           -- 30 58                                                                            -- --                                                                             -- 80 78                 ##STR104##                                                                    70% CH.sub.3 O(C.sub.2 H.sub.4 O).sub.16                                        ##STR105##                                                                     ##STR106##                                                               Standard                0.01                                                                               0   0   0   0   12  37  48  62  83                                         0.1 3   5   20  88  97  100                                                    1.0 2   75  100                                        SBO                         0   1   1   3   6   11  13  19  22                 __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________                                            PERCENT MORTALITY                       Num-                               Conc.                                                                              AT SPECIFIED DAYS                       bers                                                                               Structure                      %   1  2  3  6  8  10 14                    __________________________________________________________________________     50950                                                                              C.sub.8 F.sub.17 SO.sub.3 K    1.0 2  2  23 87 100                         10700                                                                               ##STR107##                    1.0 2  37 73 98 100                         10701                                                                               ##STR108##                    1.0 62 97 100                               01705                                                                               ##STR109##                    1.0 0  0  0  0  0  8  42                    10706                                                                               ##STR110##                    1.0 0  0  2  2  2  7  62                    10708                                                                               ##STR111##                    1.0 0  0  0  0  0  0  35                    10710                                                                               ##STR112##                    1.0 0  12 55 97 97 98 100                   10712                                                                               ##STR113##                    1.0 23 100                                  10719                                                                               ##STR114##                    1.0 0  0  3  10 33 55 85                         ##STR115##                                                                10720                                                                               ##STR116##                    1.0 10 22 33 33 33 35 43                    10722                                                                               ##STR117##                    1.0 0  0  0  0  2  3  5                     10723                                                                               ##STR118##                    1.0 0  0  0  0  0  0  0                     10724                                                                               ##STR119##                    1.0 0  0  2  7  7  10 12                    10725                                                                               ##STR120##                    1.0 0  0  2  2  3  5  8                     10726                                                                               ##STR121##                    1.0 0  0  0  0  0  2  5                     10727                                                                              C.sub.8 F.sub.17 SO.sub.3 H    1.0 0  37 62 95 100                         10728                                                                              C.sub.6 F.sub.13 SO.sub.3 H    1.0 15 77 95 100                            10729                                                                               ##STR122##                    1.0 0  0  0  22 40 58 90                    10730                                                                               ##STR123##                    1.0 0  0  0  0  2  12 77                    10731                                                                              C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.4 OH).sub.2                                                         1.0 0  0  0  0  0  25 57                    10732                                                                               ##STR124##                    1.0 0  0  0  0  0  0  2                     10734                                                                               ##STR125##                    1.0 0  0  0  2  2  2  5                     10738                                                                               ##STR126##                    1.0 0  0  2  2  2  7  10                    10739                                                                               ##STR127##                    1.0 0  0  0  2  3  17 35                    10740                                                                               ##STR128##                    1.0 0  0  0  0  2  2  2                     10743                                                                               ##STR129##                    1.0 0  2  2  15 27 42 57                    10748                                                                               ##STR130##                    1.0 0  0  0  2  3  13 63                    10750                                                                              C.sub.8 F.sub.17 SO.sub.3.sup.- + N(C.sub.2 H.sub.5).sub.4                                                    1.0 10 47 95 100                            10752                                                                              FCH.sub.2 SO.sub.2 NH.sub.2    1.0 0  0  0  2  5  17 45                    10754                                                                              CF.sub.3 CH.sub.2 SO.sub.2 NH.sub.2                                                                           1.0 0  0  0  0  0  2  18                    --  Copolymer of                                                                    ##STR131##                    1.0 0  7  12 20 20 25 52 62                      ##STR132##                                                                --  50% of Copolymer                                                                ##STR133##                    1.0 0  2  2  10 13 18 40 73                      ##STR134##                                                                     ##STR135##                                                                Standard                           1.0 0  100                                  Honey:Water                            0  0  0  0  0  1  1                     __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________                    Percent worker mortality after following                                       days of initial exposure to bait                                Number                                                                              Structure 2 10  14  16  23  26                                            __________________________________________________________________________     29757                                                                                ##STR136##                                                                              40                                                                               87  95 QD                                                     29757          10                                                                               50  75  92 QD                                                 29758                                                                                ##STR137##                                                                              10                                                                               30  50  75  90  92 QD                                         29758           5                                                                               28  35 QD                                                     29759                                                                               C.sub.8 F.sub.17 SO.sub.2 NH.sub.2                                                       15                                                                               50  65 QD                                                     29759           8                                                                               25  30  30  50 QD                                             29778                                                                                ##STR138##                                                                               0                                                                               10  35  50 QD                                                 29778           0                                                                               15 QD                                                         Control         0                                                                                1   2   2   2   2 CN                                         Control         0                                                                                2   3   3   5   5 CN                                         __________________________________________________________________________

                  TABLE 5                                                          ______________________________________                                         Number  Structure      % Mortality After 3 Days                                ______________________________________                                         29756                                                                                   ##STR139##    0                                                       29757                                                                                   ##STR140##    0                                                       29758                                                                                   ##STR141##    0                                                       29759   C.sub.8 F.sub.17 SO.sub.2 NH.sub.2                                                            80                                                      29778                                                                                   ##STR142##    60                                                      Untreated Fly Food 0                                                           ______________________________________                                    

                  TABLE 6                                                          ______________________________________                                         Conc.        Population Index                                                  Treatment                                                                              %        Pre-treatment                                                                             6 weeks % Reduction                                ______________________________________                                         Untreated        305        305     0                                                           130        155     0                                                           105        185     0                                          Standard                                                                               1        120        19      84                                                          140         0      100                                                         255        15      94                                         29758   1        170         0      100                                                         190         7      96                                                          170         0      100                                        29757   1        150         0      100                                                         160        48      70                                                          160        32      80                                         29759   2.5      195         2      99                                                          180         0      100                                                         175        25      86                                         29759   1        165         0      100                                                         195        25      87                                                          180        81      55                                         ______________________________________                                    

                  TABLE 7                                                          ______________________________________                                                    Percent Mortality After Indicated Days                              Treatment    1       2       3     7     10                                    ______________________________________                                         29756        0        0       0     60   100                                                0        0      20    100                                         29757        0       10      30     90   100                                                0       40      40    100                                         29758        0       30      40     80   100                                                0       20      30     90   100                                   29759        20      50      90    100                                                      30      80      90    100                                         29778        0       20      40    100                                                      0       50      80    100                                         Standard     100                                                                            100                                                               Cornmeal-Powdered                                                                           0        0       0     0     0                                    Sugar Mixture                                                                               0        0       0     0     0                                    ______________________________________                                    

                  TABLE 8                                                          ______________________________________                                                    Percent Mortality After Indicated Days                              Treatment    1       2       3     7     10                                    ______________________________________                                         29756        44      88      100                                                            56      100                                                                    68      88       96   100                                                      68      88      100                                               29757        88      100                                                                    92      96      100                                                            92      92      100                                                            88      96       96   100                                         29758        84      84       92   100                                                      80      92      100                                                            76      88       96   100                                                      88      92       96   100                                         29759        84      92      100                                                            96      96      100                                                            100                                                                            96      100                                                       29778        100                                                                            92      96      100                                                            96      96      100                                                            96      100                                                       Standard     100                                                                            92      96       96    96   100                                                100                                                                            100                                                               Cornmeal-powdered                                                                            0       0       0     0    0                                     Sugar Mixture                                                                                0       0       0     0    0                                                   0       0       0     0    0                                                   0       0       0     0    0                                     ______________________________________                                    

                  TABLE 9                                                          ______________________________________                                                      Lethal Concentration (ppm)                                        Chemical Code No.                                                                             LC-50      LC-90                                                ______________________________________                                         29756          0.0167     0.0486                                               29757          .0054      0.0200                                               29758          .0067      .0274                                                29759          .0029      .0081                                                29778          .0209      .0374                                                Control        .0016      .0069                                                ______________________________________                                    

                  TABLE 10                                                         ______________________________________                                         Chemical Code                                                                            % Mortality After 24 hrs., Conc. (ppm)                               No.       10       1.0     0.1    0.01  0.001                                  ______________________________________                                         29756     100      96      0                                                   29757     100      96      34                                                  29758     100      82      78                                                  29759     100      16      0                                                   29778      44      22      0                                                   Control                           98    38                                     ______________________________________                                     

We claim:
 1. A method for the control of a population of ants comprising the steps of:(a) providing to said ants a formulation comprising:(1) an effective amount of a toxicant substance or mixture of substances having the structural formula:

    CF.sub.3 (CF.sub.2).sub.x --SO.sub.2 --OR

wherein x=0 to 19; R is selected from the group consisting of H, alkaline earth metal, alkali metal, organic amine cation containing not more than 20 carbon atoms and ammonium cation; and (2) a attractant bait component for ants, said attractant bait being in an amount and of a type which when combined with said toxicant substances entices said ants to ingest said toxicant substance; and (b) permitting said ants to ingest said formulation such that said ants are killed by the delayed effect of said ingested toxicant substance and said toxicant substance is distributed to other members of said population of ants.
 2. The method of claim 1, wherein R is selected from the group consisting of lithium, sodium, and potassium.
 3. The method of claim 1, wherein R is selected from the group consisting of barium, calcium, and magnesium.
 4. The method of claim 1, wherein x=4 to
 19. 5. A method for the control of a population of cockroaches comprising the steps of:(a) providing to said cockroaches a formulation comprising: (1) an effective amount of a toxicant substance or mixture of substances having the structural formula:

    CF.sub.3 (CF.sub.2).sub.x --SO.sub.2 --OR

` wherein x=0 to 19; R is selected from the group consisting of H, alkaline earth metal, alkali metal, organic amine cation containing not more than 20 carbon atoms and ammonium cation; and (2) a bait component for cockroaches, said bait being in an amount and of a type which when combined with said toxicant substance entices said cockroaches to ingest said toxicant substance; and (b) permitting said cockroaches to ingest said formulation such that said cockroaches are killed by the delayed effect of said ingested toxicant substance and said toxicant substance is distributed to other members of said population.
 6. The method of claim 5, wherein R is selected from the group consisting of lithium, sodium, and potassium.
 7. The method of claim 5, wherein R is selected from the group cosisting of barium, calcium, and magnesium.
 8. The method of claim 5, wherein x=4 to
 19. 